JPH03231746A - Processing method for silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To increase the efficiency of processing by discharging processing solns. at the time of nonprocessing so that processing chambers through which a photosensitive material passes first and last in a continuous processing course are made empty. CONSTITUTION:Plural processing chambers connected with narrow passes are arranged in a continuous processing course. Two or more kinds of processing solns. having different compsns. are fed from different positions 11, 15 of the course and discharged from a discharge outlet 120 set at the middle of the course. At the time of nonprocessing, the processing solns. are discharged so that processing chambers through which a silver halide photosensitive material passes first and last in the course are made empty. The efficiency of processing is increased, plural kinds of photosensitive materials can be processed in the same tank and the size of a device can be reduced.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a method for processing silver halide photosensitive materials.

<Prior art> Silver halide photosensitive materials (hereinafter referred to as photosensitive materials) are
After exposure, it is processed through steps such as development, desilvering, washing with water, and stabilization. A developer is used for development, a bleach solution, a bleach-fix solution, and a fixer are used for desilvering, and tap water or ion exchange water is used for washing.
Stabilizing solutions are used in each stabilization process. The temperature of each processing solution is usually adjusted to 30 to 40°C, and the photosensitive material is immersed in these processing solutions to be processed.

A plurality of processing tanks are installed in parallel, and the photosensitive material is sequentially transported between the processing tanks.

Usually, a processing device such as an automatic processor is used for such processing.

In such cases, in recent years there has been a demand for environmental conservation and resource saving, and it is desired to reduce the amount of each processing liquid used.

On the other hand, with the development of small-scale processing systems called minilabs, photosensitive materials are now being processed at stores such as photo shops, and there is a desire for smaller devices.

In view of the above-mentioned circumstances, the present applicant has previously developed a system that includes ``a plurality of cleaning chambers formed of block-shaped members and sequentially connected by narrow passages, and a photosensitive material passing through each of the cleaning chambers sequentially. (Japanese Patent Application No. 1-27034).

In addition, we have also proposed a photosensitive material processing device that can be applied to processing other than cleaning, such as development and desilvering (
(Japanese Patent Application No. 1-90422) This method has the advantage that the apparatus can be made smaller and the processing efficiency is improved, so that the amount of processing liquid used can be reduced.

However, although these devices certainly offer the above-mentioned advantages over conventional devices, the processing liquids filled in each processing chamber in the same tank have at least the same function, and It was not possible to perform multiple treatments.

For this reason, the present applicant further proposed that, in the above-mentioned photosensitive material processing apparatus, at least one drain port is provided at a position other than the processing chamber through which the photosensitive material first passes and the processing chamber through which it passes last. (Patent Application Hei 1)
(No. 99855) With this product, by changing the installation position and number of drain ports, it is possible to perform a plurality of treatments in the same tank.

Therefore, the effect of reducing the amount of processing liquid used and making the device smaller is even greater.

By the way, in the processing of color photosensitive materials, the desilvering treatment that is performed after color development is an important processing step.In particular, color photosensitive materials for photography such as color negative film are difficult to desilver, so bleaching is necessary. It is common to use a plurality of processing baths, such as fixed fixing, bleach-bleach fixing, and fixed fixing.

For this reason, it has conventionally been necessary to use a plurality of treatment baths depending on the type of treatment bath, which has been the biggest bottleneck in terms of miniaturization of the apparatus.

Therefore, it is extremely effective to apply the apparatus described in the earlier Japanese Patent Application No. 1-99855 to desilvering treatment using a plurality of treatment baths, and the present applicant has previously proposed that (Japanese Patent Application Nos. 1-133395, 1-212790, etc.) However, such desilvering treatment, furthermore, the treatment including water washing and stabilization after this desilvering treatment, etc. ．． %I Product A
＋/rI value axis also ++n J & input w v −+ 21
+llQ Tei discovered that if so-called slow processing, in which a small amount of light-sensitive material is processed, is continued for a long period of time, sufficient photographic properties cannot be obtained (in particular, the occurrence of desilvering defects becomes significant).

<Problems to be Solved by the Invention> An object of the present invention is to improve processing efficiency, reduce the amount of processing liquid used, and downsize the apparatus, and to It is an object of the present invention to provide a method for processing a silver halide photosensitive material, which allows obtaining images with good photographic properties even under processing conditions where the amount of processing is small.

Means to solve problems〉 The above object is achieved by the configuration (1) below.

(1) In a continuous processing path in which a plurality of processing chambers are sequentially connected through narrow passages, two or more different compositions are processed from different positions in the continuous processing path.
i & meeting 1. The silver halide photosensitive material is drained from a drain port installed in the middle of the continuous processing path, and the continuous processing path is filled with processing solutions of different compositions to process the exposed silver halide photosensitive material. A method for processing a material, which comprises draining liquid so that a processing chamber through which the silver halide photosensitive material passes first and a processing chamber through which it passes last in the continuous processing path are empty when unprocessed. A method for processing a silver halide photosensitive material, characterized by:

<Operation> In the present invention, two or more processing liquids having different compositions are supplied from different positions of the continuous processing path into a continuous processing path in which a plurality of processing chambers are sequentially connected through narrow passages. At the same time, the liquid is drained from a drain port installed in the middle of the continuous processing path. As a result, the continuous processing path is filled with processing liquids having different compositions.

That is, a plurality of treatments can be performed in the same tank, and the device can be made smaller.

In addition, dead space in the processing tank can be eliminated,
Processing efficiency is improved, the amount of processing liquid used can be reduced, and the device is further downsized.

In such a case, if left untreated, the processing liquids in each processing chamber will mix with each other. Therefore, even if the processing liquid is replenished at a predetermined time after processing is restarted, the processing composition will differ from the initially preferred processing composition, and the photographic performance of the resulting image will deteriorate.

Therefore, in the present invention, when unprocessed, the processing chamber through which the silver halide photosensitive material passes first in the continuous processing path and the processing chamber through which it passes last are kept in an empty state where they are not substantially filled with processing liquid. Drain as much as possible.

As a result, when processing is restarted, a small amount of fresh processing solution is supplied, ensuring good photographic performance.

In addition, since the replenishment amount only increases by about - room,
The amount of processing liquid used does not increase significantly.

Such an effect is large in so-called slow processing in which the amount of photosensitive material processed is small.

<Specific configuration> Hereinafter, a specific configuration of the present invention will be explained.

FIGS. 1 and 2 show an example of the structure of a processing apparatus used to carry out the method of processing silver halide photosensitive materials of the present invention.

Fig. 1 shows the cross-sectional side view, and Fig. 2 shows the ■■ in Fig. 1.
It is a sectional view taken along the line -■.

As shown in these figures, the processing apparatus 1 includes a vertically long processing tank 2 having a predetermined volume. In this processing tank 2, there are block-shaped members (hereinafter referred to as block bodies) 4 and 5 installed between the side plates 31 and 32 of the rack 3. These block bodies 4.5 are made of, for example, polyethylene, polypropylene , polyphenylene oxide (PPO
), plastics such as ABS resin, phenol resin, polyester resin, polyurethane resin, ceramics such as alumina, or various metals such as stainless steel and titanium. In particular, it is preferably made of plastic such as polypropylene, PPO, ABS resin, etc. because it has excellent moldability, is lightweight, and has sufficient strength.

Moreover, although the block body 4.5 is a solid member in the illustrated example, it may be configured as a hollow member (manufactured by blow molding, for example).

The block body 4 is inserted inside the block body 5, and in this inserted state, the silver halide photosensitive material (
A space 5, which is a space for processing S (hereinafter sometimes abbreviated as photosensitive material), is formed. In addition, the adjacent processing chamber 6
Between A and 6B, 6B and 60. 6C and 6D, and 6D and 6E, there are narrow passages 71, 72, . . . that connect the image processing chambers.
73 and 74 are formed.

Further, a similar passage 75J3 for carrying in and carrying out the photosensitive material S is provided at the upper part of the processing chambers 6A and 6E, respectively.
and 76 are formed. The width of these passages 71 to 76 is preferably about 5 to 40 times the thickness of the photosensitive material S.

With such a path width, the photosensitive material S can be conveyed without any trouble.

In addition, in order to further improve conveyance, the passages 71 to 76
The inner wall surface may be subjected to water repellent treatment or the like.

The widths of the passages 71 to 76 are the same as described above even when the passageway shielding means described later is not provided, but in this case, it is preferable that the length of the passages be relatively long.

The continuous processing path in the present invention is constituted by processing chambers 6A to 6E and passages 71 to 76.

Near the center of the processing chambers 6A, 6B, 6D and 6E,
One pair of transport rollers 8 is installed in each case, and three pairs of transport rollers 8 are installed in the processing chamber 6C. Further, a pair of conveyance rollers 8 are installed near the photosensitive material entrance of the passage 75 and near the photosensitive material exit of the passage 76, respectively.

Each of these conveyance rollers 8 is pivotally supported by the block body 4 or 5, and one or both of the pair of rollers is driven to rotate so that the photosensitive material S is conveyed with the photosensitive material sandwiched between the rollers. It has become. As shown in FIG. 2, the driving mechanism of the conveyance rollers 8 includes a bevel gear 83 fixed at a predetermined position on a main shaft 82 that is vertically supported in the figure, and one end of the rotating shaft 81 of each conveyance roller 8. Each transport roller 8 is rotated by meshing with a bevel gear 84 fixed to the main shaft 82 and rotating the main shaft 82 in a predetermined direction by the operation of a drive source (not shown) such as a motor.

In this case, since the rotating shaft 81a of the conveyance roller 8 at the top is at a position shifted from the main shaft 82, the driven shaft is supported parallel to the main shaft 82 via a gear train including a gear 85 fixed to the main shaft 82. A bevel gear 83 fixed to the driven shaft 86 and a bevel gear 84 fixed to one end of the rotating shaft 81a are engaged with each other to rotate the rotating shaft 81a. Further, a gear 87 is fixed to the rotating shaft 81a inside a bevel gear 84, and by meshing the gear 87 with a gear 88 fixed to one end of the rotating shaft 81b of the other conveying roller, both conveying rollers are driven and rotated at the same time.

The transport rollers 8 in each processing chamber are configured such that one roller is driven to rotate, and the other roller is driven to rotate when the circumferential surfaces of both rollers come into contact with each other. In addition, it is preferable that the configuration in which both rollers are connected by a gear to drive and rotate both rollers, and the material constituting each of the conveying rollers 8 has durability and chemical resistance to the processing liquid, such as , neorene, various rubbers such as EPT rubber, elastomers such as Sunbrain, Thermolan, Hytrel, etc. Hard vinyl chloride, polypropylene, polyethylene, ABS resin, PPO, nylon, POM, phenol resin, silicone resin, various resins such as Teflon, alumina, etc. Ceramics, stainless steel, titanium, metals having corrosion resistance such as Hastelloy, or a combination thereof can be used.

Pairs of guides 9 for guiding the photosensitive material S are installed near the top and bottom of the transport rollers 8 in the processing chambers 6A, 6B, 6D, and 6E.

Further, a reversing guide 10 is installed between the conveying rollers 8 in the processing chamber 6C, which is curved in an arc shape and changes the direction of the photosensitive material S along this curved portion.

It is made of a plastic or metal plate, and openings 90 passing through the guide are formed almost uniformly. This opening 90
The presence of the treatment liquid Q allows the treatment liquid Q to flow and promotes circulation, thereby increasing the treatment efficiency.

The guides 9 and 10, the conveyance roller 8, and its drive system constitute a conveyance means for conveying the photosensitive material S along a predetermined path.

A liquid supply port 11 for supplying a bleaching liquid R3 is installed near the upper liquid level of the processing chamber 6A, which is located at the forefront through which the photosensitive material S first passes in the continuous processing path. Further, a liquid supply port 15 for supplying the fixing liquid R2 is installed in the processing chamber 6E at the last stage.

In the processing chamber 6C located approximately in the middle of the continuous processing path, there is installed a drain pipe 12 for discharging the overflow of the bleaching solution and the fixing solution that has essentially become a bleach-fixing solution. . That is, the drain port 120 of the drain pipe 12 is installed in the processing chamber 6C, and the overflow is discharged from the opening 121 of the drain pipe 12.

This drain pipe 12 is located at a position where the liquid level L is maintained during processing, while when no processing is being performed, the processing liquid is substantially kept in the first processing chamber 6A and the last processing chamber 6E. The opening 12 is set at a position that maintains a liquid level (for example, liquid level L) that is not filled with water.
The structure is such that the position of 1 changes.

As such, for example, as shown in FIGS. 1 and 3, the drain pipe 12 is composed of a first pipe 12A and a second pipe 12B having a smaller pipe diameter than this pipe 12A, One example is one in which the tube 12B is housed so that it can move up and down within the tube 12A.

That is, in this case, as shown in FIG.
By moving up and down in the direction, the position of the opening 121 comes to maintain the liquid level L1 or L2.

In this case, the position of the opening 121 may be moved by, for example, driving a step motor, a cylinder, or the like in response to processing signals for the photosensitive material.

Alternatively, an opening provided in the middle of the drain pipe 12 may be opened and closed.

Valves 13a8 and 13b are installed at the connection portions of the processing chambers 6A to 6E with the passages 71 to 76 as shielding means for shielding (sealing) these portions when the photosensitive material S does not pass through. As shown in FIG. 2, these valves 13a and 13b both have a roller shape with a reduced diameter (conical shape) at both ends, but the configurations of the valves 13a and 13b are different.

The valve 13a has a specific gravity smaller than that of the processing liquid (therefore, it floats due to buoyancy and shields the upper part of each processing chamber 6A to 6E. On the other hand, the valve 13b has a specific gravity smaller than that of the processing liquid). Thick (therefore, it settles, each processing chamber 6A, 6B
, 6D, and 6E.

This can be done by selecting these constituent materials. For example, when the valves 13a and 13b are solid rollers, the constituent material of the valve 13a is foamed polypropylene, foamed P
P01 foamed ABS or the like may be used as a constituent material of the valve 13b, such as hard vinyl chloride, ABS resin, PPO, or the like.

Further, even if the valve 13a is made of a material having a higher specific gravity than the processing liquid, buoyancy can be provided by making the valve 13a a hollow roller as shown.

Furthermore, the specific gravity of the valve 13b as a whole can be increased by inserting a core material such as a metal (not shown) into the valve 13b if necessary.

From the viewpoint of improving the shielding properties of the passages 71 to 76, it is preferable that the right valves 13a and 13b are made of an elastic body such as silicone rubber or various other elastomers, or that the valves are made of these materials.

These valves 13a and 13b block the entrances and exits of the passages 71 to 76 when the photosensitive material S is not passing through, but when the photosensitive material S is passing through, they are pressed by the photosensitive material S and the block body 4. The photosensitive material S can be rolled along the inclined surfaces 14a and 14b formed in the photosensitive material S. After the photosensitive material S has passed, the valves 13a and 13b return to their original positions, again blocking the entrances and exits of the passages 71 to 76.

Note that the shielding means is not limited to the above-mentioned valve, but includes, for example, a fluid shutter using a fluid (paraffin, liquid crystal, oil, etc.) described in Japanese Patent Application No. 142464/1982, a shutter using magnetic fluid, and a shutter using a magnetic fluid, as described in Japanese Patent Application No. 1983-142464. 947
55, a squeegee type shielding member described in Japanese Patent Application No. 63-94756, and a crank mechanism shown in FIG. 2 of Japanese Patent Application No. 01-27034. A shielding plate that moves according to the pressure, or other gaskets, gaskets, labyrinths, etc. may be used.

Further, in the present invention, it is not necessary to provide a shielding means, and even in this case, the same shielding effect as described above can be obtained between each processing chamber.

In addition, in the above, the volume per processing chamber is 20~
It may be about 3000 mj, preferably about 60 to 900 mj.

Next, the usage and operation of the processing device having the above configuration will be explained.

When starting the processing of the photosensitive material S, the bleaching liquid R, is supplied from the liquid supply port 11, and the fixing liquid R2 is supplied from the liquid supply port 15, respectively.

The supply of the bleaching solution R and the fixing solution R2 is continued even during processing, and the bleaching solution R and the fixing solution R2 are supplied as replenishing solutions.

In this way, the bleaching solution and the fixing solution are supplied to the processing chamber 6C.
By overflowing to maintain the liquid level L1 from 1 to 6, each of the processing chambers 6A to 6E is filled with a processing liquid having substantially the following desilvering ability.

Processing chamber 6A...Bleach solution processing chamber 6B...Bleach-fix solution processing chamber 6C containing many bleaching components
...Bleach-fix solution processing chamber 6D...Bleach-fix solution processing chamber 6E containing many fixing components
...Fixer As mentioned above, the reason why each processing chamber can be filled with a processing solution having desilvering ability is based on the above-mentioned structural characteristics. This is because there is almost no liquid flow between the processing chambers (and there is only a slight flow during processing).

Here, "there is almost no flow" means that the amount of processing liquid transferred between processing chambers is so small that it can be ignored, for example, the amount of processing liquid transferred is less than 2 m17 minutes. Refers to the case.

In addition, "there is only a small amount of circulation" means that the amount of processing solution transferred between processing chambers is about the same amount as the supply amount of replenisher solution or less than that, e.g. 'rXl? m m J, < +-Q r+ -a
/ It is preferable to set it to 71 times.

At this time, the bleaching solution moves in the same direction as the transport direction of the photosensitive material S (parallel flow), and the fixing solution moves in the opposite direction (counterflow).

In this way, the bleaching efficiency is improved by making the flow of the bleaching solution a parallel flow.

Furthermore, the flow of the fixing solution is referred to as a counterflow, but in bleach-fixing processing, only fixing proceeds in the unexposed and undeveloped areas, and in the developed areas, bleaching proceeds first and then fixing proceeds. It is preferable from the viewpoint of processing efficiency to perform a substantial bleaching process in the processing chamber 6A (first chamber) and a substantial fixing process in the processing chamber 6E (fifth chamber), and in fact, the processing efficiency is improved.

Furthermore, since the processing chamber 6E is substantially filled with the fixing solution and no bleaching agent component is present, the washing load can be significantly reduced in the next step of washing.

'IL-m し A I-+ R* 口1i
1--)-11,% In a continuous processing path that includes physical processing, it is possible to perform a bleaching process in the first processing chamber and at least a fixing process in the last processing chamber. , and a bleach-fixing process can be performed in a processing chamber provided with a drainage port in the intermediate processing chamber.

In addition to such bleaching, bleach-fixing, and fixing processes, the intermediate processing chamber other than those mentioned above stores a bleach-fix solution similar to a bleach solution and a bleach-fix solution similar to a fix solution. Therefore, desilvering treatment using such a treatment liquid is also possible.

As described above, in the present invention, a desilvering process including at least a bleaching-bleach-fixing process can be performed.

Conventionally, such a treatment requires a minimum of three baths, but in the present invention, it can be carried out efficiently with only one treatment bath.

This efficiency is due to the time required for crossover between treatment tanks (air time) compared to when using multiple treatment tanks.
This is also due to the fact that the process is no longer necessary, leading to a reduction in processing time.

Therefore, from these points of view, the apparatus can be downsized, and since the desilvering efficiency is improved, the amount of replenishment of the bleaching solution and fixing solution to be supplied can be reduced.

The improvement in processing efficiency is also due to the fact that there is no contact between the photosensitive material S and the atmosphere during processing.

The above-mentioned bleaching solution R1 and fixing solution R2 may be supplied as replenishers depending on the processing signal of the photosensitive material S, for example, at the same time as the processing signal is received, or after a certain period of time, etc. .

When the photosensitive material S is not processed, the above-mentioned replenishment is not only stopped as in the normal case (as described above, the opening 121 of the liquid drain pipe 12 is moved to a position where the liquid level L2 is maintained). By draining the liquid from the processing chamber 6C, the processing chambers 6A and 6E become empty and are not substantially filled with processing liquid.

In this case, in the illustrated example, the liquid is drained to maintain the liquid level L2, but depending on the case, the processing chambers 6A, 6E
The processing liquid may be drained so that a portion of the processing liquid remains in the processing chambers 6B and 6D, or may be drained so that a portion of the processing liquid remains in the processing chambers 6B and 6D.

Further, the movement of the opening 121 of the drain pipe 12 to empty the processing chambers 6A and 6E may be performed when no processing signal of the photosensitive material S is received for one hour or more.

When the processing signal for the photosensitive material S is received again, the opening 121 of the drain pipe 12 returns to the position where the liquid level L1 is maintained, and the fresh bleaching solution supplied to the processing chamber 6A and the processing signal are removed. The photosensitive material S will be processed with the fresh fixer supplied to the chamber 6E.

In particular, by changing the drainage position in this way,
In so-called slow processing (processing amount per day of 0.01 to 0.5 m'') where the amount of sensitive material processed is small, if the processing chambers 6A and 6E are filled with processing liquid when not processed,
Processing liquid with deteriorated processing performance is stored in the processing chamber as is, and even if fresh processing liquid is supplied when processing is restarted, it takes time to replace the deteriorated processing liquid, and sufficient photographic properties are not obtained. However, these problems have been solved, and defects such as desilvering failures are prevented, and good images can be obtained.

Among these, it is preferable to treat defective desilvering using a fresh treatment liquid at the beginning of the desilvering process because it is efficient. Further, even in the latter stage of the desilvering process, the process is further processed using a fresh processing solution, so that the efficiency of the process is further improved.

The processing using the illustrated processing apparatus is performed on the photosensitive material S after exposure and color development processing.
This desilvering treatment is followed by water washing and/or stabilization treatment.

For the subsequent processing, it is preferable to use an IJ'L pushing device as shown in FIG.

In FIG. 4, only the outlines of the processing chamber, passages, etc. are schematically shown, and the processing tank, block body, conveyance rollers, guides, etc. are omitted.

This product is similar to Figures 1 and 2, except that there is no drain pipe installed in the processing chamber located in the middle of the continuous processing path.
There is no essential difference from the processing equipment shown in the figure.
It is configured to perform washing and stabilization treatment in the same tank.

As shown in the diagram, the processing chamber at the last stage of the continuous processing path (fifth chamber)
The stabilizing liquid SB is supplied from the processing chamber (4th chamber) located at the front stage, and the washing water W is supplied from the processing chamber (4th chamber) located at the front stage.
(first chamber) The overflow is discharged from a drain port 16 provided in a narrow upper passage.

The details of such a treatment tank are described in Japanese Patent Application Nos. 1-27034, 1-25132, and 1-61707 filed by the present applicant.

In the washing step in a processing apparatus having such a configuration, the washing water flows in a direction opposite to the direction in which the photosensitive material is transported (counter flow).

Because of this flow, and because the amount of liquid movement in each processing chamber is the same as in the processing apparatus shown in Figs. 1 and 2, the ratio of the concentration of chemicals, etc. brought into each processing chamber by the photosensitive material As a result, the freshness of the washing water W in the fourth chamber is maintained, and the washing efficiency is improved.

This improvement in water washing efficiency is partly due to the fact that the photosensitive material S does not come into contact with the atmosphere during processing.

By improving the washing efficiency in this way,
The amount of replenishment of washing water can be reduced.

Furthermore, the stabilizing liquid moves from the fifth chamber to the fourth chamber, but this is rather preferable in terms of obtaining good photographic properties.

In the above description, as shown in FIGS. 1 and 2, the processing apparatus for carrying out the present invention supplies two types of processing solutions that have the same broad function of desilvering ability but have different compositions. Although the description has been given using a method that performs desilvering treatment, it is also possible to perform a treatment in which processing liquids having different functions in a broad sense are added.

An example of a processing device that implements this is the one shown in FIG.

This equipment is essentially the same as the processing equipment shown in Figures 1 and 2, except for the number of processing chambers and the installation position of the liquid supply port. Only the outline is schematically shown.

Further, as shown in the figure, nine processing chambers are installed, and hereinafter, each processing chamber will be referred to as a first chamber to a ninth chamber according to the conveyance direction of the photosensitive material S.

In the processing apparatus shown in FIG. 5, the bleaching solution BI is
2 is installed in the passage between the 4th and 5th chambers, supplying the fixing solution F from the 2nd and 6th chambers, the washing water W from the 8th chamber, and the stabilizing liquid SB from the 9th chamber. Regarding the overflow from the drain pipe 12, the position of the opening 121 of the drain pipe 12 is at the liquid level L during treatment and when not treated.

The structure is similar to that shown in FIGS. 1 and 2 in that it is configured to move so as to hold L4, and is designated by the same number.

The processing liquid filled in each processing chamber of such a processing apparatus is as follows.

1st chamber...Bleach solution 2nd chamber...Bleach-fix solution (strong bleaching activity) 3rd chamber...Bleach-fix solution close to the fixer 4th room...Bleach-fix solution (close to the fixer) (low activity) 5th chamber: Fixing solution partially mixed with bleach-fixing solution 6th chamber:
...Fixer (mostly has only fixing ability) 7th chamber... Rinse water containing stabilizer components (partially contains fixer) 8th chamber: Rinse water containing stabilizer components Part Q ′＊
! Therefore, with this product, the desilvering process including the steps of bleaching → bleach-fixing → regular maintenance, washing with water, and stabilization can be performed in the same tank, and the equipment can be made smaller. and the processing time can be shortened.

Further, in the desilvering treatment, the same effects as described above can be obtained, and furthermore, the amount of replenishment of the processing liquid including washing water can be reduced, and as a result, the amount of waste liquid is also reduced.

Furthermore, the supplied fixer F has a great effect of washing out the developing agent and oxidizing agent in the emulsion layer, and the generation of thermostin after processing is suppressed.

In addition, the washing water becomes a counter flow at this time,
Improves washing efficiency.

Further, the effects caused by the stabilizing liquid flowing from the ninth chamber to the eighth chamber are similar to those shown in FIG. 4.

Furthermore, the effect of changing the position of the opening 121 of the drain pipe 12 is similar to that shown in FIGS. In this case, treatment with fresh bleaching solution becomes possible, and occurrence of desilvering defects etc. can be prevented. On the other hand, in the ninth chamber, processing with fresh stabilizing solution is possible in such a case, and the finish of the photograph is improved.

Note that in the apparatuses shown in FIGS. 1 and 2 or the apparatus shown in FIG. 5, the volumes of the processing chambers are approximately the same in each, but the The volume of the preceding processing chamber may be smaller than that of the other processing chambers, and this is preferable in terms of improving processing efficiency.

In the above, examples have been shown in which the present invention is applied to desilvering treatment, or desilvering treatment, water washing, and stabilization treatment.
However, it is not limited to this (by changing the number of processing chambers, the installation position and number of liquid supply/drainage ports, etc., it is possible to apply it to complex processing including processing such as color development processing). .

However, the present invention is highly effective when applied to subsequent processes including desilvering treatment in the processing of color light-sensitive materials, particularly to desilvering treatment.

In addition, above, we have described the case in which processing liquid is refilled in both processing chambers that are empty when no processing is being performed, but when replenishing processing liquid in only one of the processing chambers, or in the processing chamber that is emptied, The effects of the present invention can be achieved even when replenishment is not necessarily performed.

The photosensitive material used in the present invention may be any of various color and black and white photosensitive materials. For example, color negative film, color reversal film, color photographic paper, color positive film, color reversal photographic paper, photosensitive material for plate making,
Examples include X-ray photosensitive materials, black and white negative films, black and white photographic paper, and microphotosensitive materials.

Among these, it is preferable to apply the present invention to the processing of color light-sensitive materials, particularly color light-sensitive materials for photographic use having a high emulsion content such as color negative films.Next, the processing liquid used in the present invention will be described.

The processing solution having desilvering ability in the present invention includes a bleaching solution, a bleach-fixing solution, and a fixing solution.

The bleaching agent used in the bleach or bleach-fix solution is a ferric ion complex or a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or a salt thereof. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, and lithium, and examples of water-soluble amines include alkylamines such as methylamine, diethylamine, triethylamine, and butylamine, ring amines such as cyclohexylamine, and fr aliamines such as aniline and m-toluidine. - Ruatan - Water is a heterocyclic amine such as pyridine, morpholine, piperazine.

Typical examples of chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetic acid tetra(
trimethylammonium) salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid trisodium salt, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N-(β-oxyethyl)-N.

N', N'-triacetic acid, ethylenediamine-N-(β
-oxyethyl)-N,N',N'triacetic acid trisodium salt, ethylenediamine-N-(β-oxyethyl)-N,N'N°-triacetic acid triammonium salt, 1
．． 2-diaminopropane-tetraacetic acid, 1,2-diaminopropane-tetraacetic acid disodium salt, 1゜3-diaminopropane-tetraacetic acid, 1,3-diaminopropane-tetraacetic acid diammonium salt, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, cyclohexane Diaminetetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-N,N.

Examples include N',N'-tetramethylenephosphonic acid, 1°3-propylenediamine-N,N,N'N°-tetramethylenephosphonic acid, but are not limited to these exemplified compounds.

The iron ion complex salts may be used in the form of complex salts or as ferric salts, such as ferric sulfate, ferric silver chloride, ferric nitrate, ferric sulfate, ferric sulfate. A ferric ion complex salt may be formed in a solution using ammonium, ferric phosphate, etc. and a chelating agent such as aminopolycarboxylic acid or phosphonocarboxylic acid. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred.

The amount added is usually 0.02 to 1 mol/knotl, preferably 0.06 to 0.6 mol/ktl.

Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary.

A compound having a mercapto group or a disulfide group is
It is preferable because it has a large promoting effect, especially the U.S. patent cylinder 3.8
Preferred are the compounds described in No. 93,858, West German Patent No. 1.290,812, and JP-A-53-95630.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (
For example, a rehalogenating agent of potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodide (eg ammonium iodide) can be included.

If necessary, boric acid, borax, sodium metaborate, acetic acid,
One or more inorganic acids, organic acids and their alkali metal or ammonium salts or , ammonium nitrate, guanidine, etc. The fixing agent used in the bleach-fixing solution or fixing solution in the present invention is a known fixing agent, i.e., a thiosulfate salt such as sodium thiosulfate, ammonium thiosulfate, etc. ; Water-soluble silver halide solubilizers such as ethylene bisthioglycolic acid, thioether compounds such as 3,6-cythia-1,8-octanediol, and thioureas; one type or a mixture of two or more of these is used. can be used. Also, JP-A-51-1
A special bleach-fixing solution consisting of a combination of the fixing agent described in No. 55354 and a large amount of a halide such as potassium iodide can also be used. In the present invention,
Preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per liter is preferably 0.3 to 2 moles.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 10 are preferred, and 5 to 9 are particularly preferred.

When p)I is lower than this, the desilvering property is improved, but fatigue of the solution and leucoization of the cyan dye are promoted. On the contrary, p
When H is higher than this, desilvering is delayed and staining is likely to occur. In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g., sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), metabisulfites (e.g., sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.), etc. Contains sulfite ion-releasing compounds.

These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/liter, more preferably 0.04 to 0.40 mol/liter. As a preservative, sulfite is generally added, but other substances such as ascorbic acid, carbonyl bisulfite adducts, or carbonyl compounds may also be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

In addition to tap water, ion exchange water and the like can be used for the washing process in the present invention.

Moreover, water softeners, bactericidal agents or antifungal agents, surfactants, etc. may be added to these.

The amount of washing water can be set within a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the washing water temperature, and various other conditions. The pH of the washing water is 4-9, preferably 5-8.

The washing temperature and washing time also vary depending on the characteristics of the color photosensitive material, etc.
20 seconds to 10 minutes at 45°C, preferably 3 to 45°C
A range of 0 seconds to 5 minutes is selected.

Further, a compound having an image stabilizing function is added to the stabilizing liquid used for the stabilizing process. Examples include aldehyde compounds typified by formalin, buffers for adjusting membrane pH suitable for dye stabilization, and ammonium compounds. Furthermore, various fungicides, fungicides, surfactants, optical brighteners, hardeners, chelating agents, magnesium and bismuth compounds, and the like can be added.

The processing conditions and the like in this stabilization treatment can be set in the same manner as in the above-mentioned cleaning or water washing treatment.

In the present invention, the black and white developer used in the development process performed prior to the desilvering process includes dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N -Methyl-p-aminophenol) and other known developing agents may be used alone or in combination.

A color developer used in color development processing is generally composed of an alkaline aqueous solution containing a color developing agent.

The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N -ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N
-ethyl-N-β-methoxyethylaniline, etc.) can be used.

The developer solution may also contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants, and the like.

In addition, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, antioxidants, alkalis, etc. It may also contain agents, solubilizers, surfactants, antifoaming agents, and the like.

The processing temperature of the color developer in the present invention is 3
Preferably 0°C to 50°C, more preferably 33°C to 4°C
It is 2℃.

The first black-and-white developer used when applying reversal processing in the present invention can contain various additives that are used in black-and-white developers for processing black-and-white silver halide photosensitive materials.

The present invention can be applied to various photosensitive material processing apparatuses, such as wet-type copying machines, automatic developing machines, printer processors, video printer processors, photo print production coin machines, and color paper processing machines for plate inspection.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Using the color negative film of Sample 201 described in Example 2 of JP-A-1-259359, color was developed according to the following processing steps using a modified machine of JIgen tlFP230B for color negative manufactured by Fuji Photo Film ■. A running process was performed for one month until the cumulative replenishment amount of the developer reached 30ρ.

Processing process Processing time Processing temperature Replenishment amount Color development
3 minutes 15 seconds 37.8℃ 16mj bleaching
30 seconds 38.0℃ 5filj constant
Arrival 1 minute 38.0℃ 15mA water washing (1120 seconds 38.0℃ Water washing (2) 20 seconds 38.0℃ 201
Stable 20 seconds 38,0℃ 20r
nl drying 141 minutes 55°C Replenishment amount is 35 mm width per meter of water washing is countercurrent method from (2) to (1) The composition of the processing solution is shown below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl- Add N-β-hydroxyethylamino)-2-methylaniline sulfate solution to give pt(1,0 3,0 4,0 30,0 1,4 1,5 mg 2.4 4.5 1.01 10.05 1.1 3.2 4.9 30.0 3.6 7.2 1.0j 10.10 (Bleach solution) 1.3-Diaminopropanetetraacetic acid ferric ammonium hydrate salt 1.3-diaminopropanetetraacetate Acetic acid ammonium bromide Ammonium nitrate Aqueous ammonia (27%) Acetic acid (98%) Add water to pH Mother liquor (g) 144.0 2.8 84.0 0 10.0 51.1 1, oj 4.3 Replenisher ( g) 206.0 4.0 120.0 0 1.8 73.0 1, O! 3.4 (Fixer) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid disodium salt 1,7 Sodium sulfite 14. 0 Sodium bisulfite 10.0 Ammonium thiosulfate aqueous solution (70% weight/volume) 320.0 Add water 1.0 jpH 7.2 (Washing water) Mother liquor, replenisher Common tap water to H-type strongly acidic cation exchange resin (ROHM The calcium and magnesium ion concentrations were reduced to 3 B/j or less by passing water through a hotbed column packed with Amberlite IR-120B (manufactured by Andhaas) and OH type anion exchange resin (Amberlite IR-400). Then, 20 mg/j of sodium isocyanurate dichloride and 0.15 g/j of sodium sulfate were added.

The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (g) Surfactant 0.5 Surfactant 0.4 [Cl0H21
-0+ CHzCHzO+ ro-former triethanolamine 2.01.2-Pentisothia 0
．． 01 Zolin-3-one Methanol 0.3 Formalin (3
7%) 1.5 Water with Kada 1j pH 6.5 The product treated in this way is treated IA.

With processing IA, good photographic performance was obtained even after one month of running.

In treatment IA, the treatment time from bleaching to stabilization treatment was shortened by 10% in total as follows. This is called processing IA'.

processing time Bleach White 25 seconds Fixed arrival time 50 seconds Washing with water (1) 20 seconds Washing with water (2) 20 seconds Stability 20 seconds In this treatment IA', desilvering failure occurred.

Next, in the process IA, in a process apparatus as shown in FIG.
The bleaching to stabilization process was carried out for one month using the same process time and replenishment amount as shown below.

7's wandering 1j se L% - to the government official h delivery old banquet small amount is 3
00 mj, and only the -th chamber was set to 15 mj. The processing liquid moves at a rate of about 0.1 mj/min during non-processing.
At the time of treatment, it was about 20 mj/min.

Prior to processing, each processing solution was filled as shown in the figure, and each replenisher solution was similarly replenished during processing.

Processing time Replenishment amount Bleach 12 seconds 5mj Bleach solution from 1st chamber) Bleach-fixing 12 seconds x 3 3mj Fixer from 2nd chamber) Fixing 12 seconds x 2 1Qmg Fixer from 6th chamber) Washing
12 seconds x 2 20mA Rinsing water from the 8th room) Stable 1
2 seconds 20 mε Stable liquid from the 9th chamber) Such a process is referred to as process IB.

In this process IB, the processing time from bleaching to fixing is 72
Although the processing time was approximately 25% shorter than the 90 seconds of processing IA, there was no occurrence of desilvering defects (and good photographic performance was obtained. We were able to achieve a 10% reduction in this process.

In processing IB, processing was carried out under the same conditions as above for the first three weeks, and then continued for one month under the condition that one color negative film was processed every three days (small quantity processing). Such processing is referred to as a processing IC.

In this processed IC, desilvering failure occurred after one month of running processing.

In the processing IC, the processing device shown in FIG. When the opening 121 moves from the level L3 to the position L4 and receives the processing signal again, the opening 121 is at the liquid level L.
The liquid was replenished so that the liquid level returned to position 3 and the liquid level L3 returned, and the other processes were the same. This is called processing ID.

In this treatment ID, no defective desilvering occurred.

In the treatment ID, the treatment time from bleaching to stabilization was shortened as follows. This is called a processing IE.

Processing time Bleach: 11 seconds Bleach-fixing: 11 seconds x 3 Fixing: 11 seconds x 2 Washing with water
11 seconds x 2 stable 1
In 1-second processing IE, although the processing time from bleaching to fixing could be shortened by about 30% compared to processing IA, there was no occurrence of desilvering defects and good photographic performance was obtained.

Example 2 In the processing IC of Example 1, processing steps from bleaching to fixing were performed using the processing apparatus shown in FIGS. 1 and 2,
The processing steps of water washing and stabilization were performed using the processing apparatus shown in FIG.

However, in this case, the processing apparatus shown in FIGS. 1 and 2 has an additional liquid supply port in the second chamber, and the processing apparatus shown in FIGS. F
19, the opening 1 was fixed so that the opening 1 was in the position of the clear side and the bevel was used. Further, the volume per chamber of these processing devices is 800 mA, and the amount of liquid movement between the processing chambers is the same as that in FIG. 5.

The processing time from bleaching to stabilization and the amount of replenishment were as follows.

Processing time Replenishment amount Bleach 12 seconds
Arrival 12 seconds x 2 10mj Fixer from 5th chamber) Washing 12 seconds x 4 20rnl Washing solution from 4th chamber Stable 12 seconds 20mj Stable solution from 5th chamber) Such a process is referred to as Process 2C. In this treatment 2C, desilvering failure occurred.

In Process 2C, the processing apparatus shown in FIGS. 1 and 2 (with an additional liquid supply port as in Process 2C) was used, and the rest was as follows:
Treated in the same way.

In addition, regarding the movement between the liquid level L1 and Lz of the opening 121 of the drain pipe 12, the process tn of the floating example 1 is performed.
I went to crush it.

This is called processing 2D.

In this process 2D, although the processing time could be reduced by about 30% compared to the process IA of Example 1, no desilvering failure occurred and good photographic performance was obtained.

<Effects of the Invention> According to the present invention, the amount of processing liquid used can be reduced, and the apparatus can be made smaller.

In addition, processing efficiency is improved, processing time can be shortened, and a product with good photographic performance can be obtained even when running for a long period of time under processing conditions with a small amount of processed material.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional side view showing a configuration example of a processing apparatus according to the present invention. FIG. 2 is a sectional view taken along the line ■-■ in FIG. 1. FIG. 3 is a partial sectional view showing the structure of the drain pipe in FIG. 1. FIG. 4 is a schematic configuration diagram of a processing device used in combination with the processing device of FIG. 1. FIG. 5 is a schematic configuration diagram showing another configuration example of the processing device according to the present invention. Explanation of symbols 1...Photosensitive material processing device 2...Processing tank 3...Rack 31.32...Side plate 4.5...Block body 51...Groove 6A to 6E...Processing chamber 71 to 76... Passage 8... Conveyance roller 81... Rotating shaft 82... Main shaft 83.84... Bevel gear 85.87.88... Gear 86... Driven shaft 9... Guide 90...Opening 10...Reversing guide 11.15...Liquid supply port 12...Drainage pipe 120.16...Drainage port 121...Drainage pipe openings 13a, 13b- Valves 14a, 14b --- Inclined surface S... Photosensitive material Bβ... Bleaching solution F... Fixing solution W... Water SB... Stabilizing solution ~ L4... Liquid level

Claims (1)

[Claims] (1) While supplying two or more processing liquids with different compositions from different positions in the continuous processing path into a continuous processing path in which a plurality of processing chambers are sequentially connected through narrow passages, Processing of silver halide photosensitive materials, in which the liquid is drained from a drain port installed in the middle of a continuous processing path, and the continuous processing path is filled with processing solutions of different compositions to process the silver halide photosensitive material after exposure. The method is characterized in that when unprocessed, the processing chamber through which the silver halide photosensitive material first passes and the processing chamber through which it passes last in the continuous processing path are drained so that they are empty. A method for processing silver halide photosensitive materials.